CN108624274A - A kind of dealcoholized silicone rubber sealant and preparation method thereof - Google Patents
A kind of dealcoholized silicone rubber sealant and preparation method thereof Download PDFInfo
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- CN108624274A CN108624274A CN201810436924.4A CN201810436924A CN108624274A CN 108624274 A CN108624274 A CN 108624274A CN 201810436924 A CN201810436924 A CN 201810436924A CN 108624274 A CN108624274 A CN 108624274A
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- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
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Abstract
The present invention provides a kind of dealcoholized silicone rubber sealants, including following components：100 parts by weight of dimethyl silicone polymer；The parts by weight of 20 parts by weight of calcium carbonate~200；The parts by weight of 2 parts by weight of organosilicon cross-linking agent~12；The parts by weight of 0.05 parts by weight of catalyst~8；The parts by weight of 0.05 parts by weight of tackifier~5；The tackifier are prepared by amino coupling agent, epoxy group coupling agent and polyisocyanate compound.Compared with prior art, dealcoholized silicone rubber sealant provided by the invention uses specific tackifier, coordinates other certain content components, realizes preferable interaction, make product have preferable greenhouse curing performance and long-term storage stability, and it is excellent in adhesion, bonding persistence it is good.The experimental results showed that dealcoholized silicone rubber sealant provided by the invention, to metal, various plastics, ceramics, the materials such as glass all have good caking property, it can be used in photovoltaic module, building and the sealings such as automobile and electronic apparatus.
Description
Technical field
The present invention relates to organic silicon rubber technical fields, are to be related to a kind of dealcoholized silicone rubber sealant more specifically
And preparation method thereof.
Background technology
Organic silicon rubber glue is a kind of monocomponent room-temperature cured organic silicon rubber of thixotropic, can at room temperature with air
In moisture-curable, be elastomer after glue solidification, there is remarkable cold-and-heat resistent alternation performance, ageing-resistant performance and insulating properties
Can, while glue-line has excellent moisture-proof, antidetonation, Inverter fed motor, anti-electric creepage performance.
Currently, the constituent of room temperature curing organic silicon rubber exists a variety of and is used widely.Wherein, with hydroxyl or
The dimethyl silicone polymer and alkoxy silane of alkoxysilyl group sealing end are primary raw material, and are urged in organic titanium, zirconium, tin compound
In the presence of agent, the cured dealcoholized type room temperature vulcanized silicone rubber constituent of alcohol compound is released, with no bromine, to metal class
The advantages that corrosion-free, to be widely used in the sealing material of electric appliance and electronic and the sealant etc. of bonding agent, structure material.But
It is that there are still some problems for dealcoholized silicone rubber sealant：Due in dealcoholized type room temperature vulcanized silicone rubber micro-moisture and
Free alcohol occurs chain in the presence of organo-metallic catalyst, with polysiloxanes and cuts and equilibration reaction, forms short chain and nothing
It is crosslinked (the CH of function3O)(CH3)2SiO1/2The products such as end group make its curability can be with the extension of storage time with transitivity
And be gradually reduced and even disappear, it is especially poor to the cementability of the base materials such as glass, Plastic, metal class.Such as patent US5053442
Using alkoxy end-capped polysiloxanes as base rubber, alkoxy silane is crosslinking agent, and using organic titanium as catalyst, has been made organic
Silicone sealant material；The material non-toxic is tasteless, but that there are Storage periods is short, and cementability is not strong, the problem of hardening time length.For another example specially
Sharp CN101012364 is base rubber using end trimethoxy siloxane, and metatitanic acid fat chelate is the system of catalyst, although improving
The stability and cementability of product, but still there are cementability deficiency, Storage period short problems.In addition, patent
CN102618209A discloses a kind of photovoltaic module single-component dealcoholization-type fluid sealant and its preparation process, fluid sealant have good
Good anti-flammability is corrosion-free, but equally exists cementability deficiency, the short problem of Storage period.Therefore, dealcoholized silicone rubber sealant
There are the problem of limit its further applying in more extensive use.
In this regard, researcher has carried out a variety of trials, to improve cementability and the storage of dealcoholized type room temperature vulcanized silicone rubber
Deposit stability.Currently, the method that the prior art generally uses addition hydroxyl scavenger, to effectively prevent dealcoholized type room temperature vulcanized silicon
The hydroxyl scavenger of the generation of free alcohol in rubber, most common of which is hexamethyldisilazane；But hexamethyldisilazane
It can act on and release ammonia, the materials such as copper are caused to corrode, while influence the curing performance of dealcoholized type room temperature vulcanized silicone rubber, especially
It can be largely influenced on curing performance and adhesive property generation in the dealcoholized silicone rubber that Ti is catalyst.
Invention content
In view of this, the purpose of the present invention is to provide a kind of dealcoholized silicone rubber sealant and preparation method thereof, this hair
The dealcoholized silicone rubber sealant of bright offer has preferable greenhouse curing performance and long-term storage stability, and cementability
It is excellent, bonding persistence it is good.
The present invention provides a kind of dealcoholized silicone rubber sealants, including following components：
100 parts by weight of dimethyl silicone polymer；
The parts by weight of 20 parts by weight of calcium carbonate~200；
The parts by weight of 2 parts by weight of organosilicon cross-linking agent~12；
The parts by weight of 0.05 parts by weight of catalyst~8；
The parts by weight of 0.05 parts by weight of tackifier~5；
The tackifier are prepared by amino coupling agent, epoxy group coupling agent and polyisocyanate compound.
Preferably, the dimethyl silicone polymer includes general formula shown in the compound of general formula and/or formula (II) shown in formula (I)
Compound；
HO(SiMe2O)nH formulas (I)；
(R2O)3-mR1 mSi-Z-(SiMe2O)nSiMe2-Z-SiR1 m(OR2)3-mFormula (II)；
Wherein, n be when the viscosity of dimethyl silicone polymer being made to be 200mPas~1000000mPas at 25 DEG C just
Number；R1And R2It is independent to be selected from monovalent hydrocarbon or alkoxyalkyl；M=0 or 1；Z is oxygen or bivalent hydrocarbon radical.
Preferably, the dimethyl silicone polymer further includes the polydimethylsiloxanes of Alpha-hydroxy-ω-trimethyl silicon substrate sealing end
The dimethyl silicone polymer of alkane and/or α-triethoxy silicon substrate ethyl-ω-trimethyl silicon substrate sealing end.
Preferably, the organosilicon cross-linking agent is selected from methyltrimethoxysilane, vinyltrimethoxysilane, methyl three
Ethoxysilane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, trimethoxysilane, isobutyl group three
It is one or more in Ethoxysilane, methyl orthosilicate and ethyl orthosilicate.
Preferably, the amino coupling agent is selected from aminopropyl trimethoxysilane, aminopropyl triethoxysilane, γ-ammonia
Ethylaminopropyl trimethoxy silane, γ-aminoethylaminopropyl triethoxysilane, bis- [3- (triethoxysilicane) propyl] amine,
Bis- (3- trimethoxy-silylpropyls) amine, bis- [3- (trimethoxy silicon substrate) propyl] ethylenediamines and bis- [3- (triethoxysilicanes
Base) propyl] ethylenediamine it is one or more.
Preferably, the epoxy group coupling agent is sweet selected from γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-shrink
Oily ether oxygen propyl triethoxysilane, γ-glycidyl ether oxygen propyl methyldiethoxysilane, γ-glycidyl ether oxygen third
Ylmethyl dimethoxysilane, β-(3,4- 7-oxa-bicyclo[4.1.0s) ethyl trimethoxy silane it is one or more.
Preferably, the polyisocyanate compound is selected from toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, 1,
It is one or more in hexamethylene-diisocyanate, hexamethylene diisocyanate tripolymer and isoflurane chalcone diisocyanate.
Preferably, the tackifier are 1 by molar ratio：2：The amino coupling agent of (0.2~3), epoxy group coupling agent and more
Isocyanate compound is prepared.
The present invention also provides a kind of preparation methods of the dealcoholized silicone rubber sealant described in above-mentioned technical proposal, including
Following steps：
A) amino coupling agent, epoxy group coupling agent and polyisocyanate compound are mixed, is reacted, is viscosified
Agent；
B) tackifier for obtaining dimethyl silicone polymer, calcium carbonate, organosilicon cross-linking agent, catalyst and step a) are mixed
It closes, dealcoholized silicone rubber sealant is obtained after discharging.
Preferably, the temperature reacted described in step a) is 20 DEG C~60 DEG C, and the time is 48h~680h.
The present invention provides a kind of dealcoholized silicone rubber sealants, including following components：100 weight of dimethyl silicone polymer
Part；The parts by weight of 20 parts by weight of calcium carbonate~200；The parts by weight of 2 parts by weight of organosilicon cross-linking agent~12；0.05 parts by weight of catalyst~
8 parts by weight；The parts by weight of 0.05 parts by weight of tackifier~5；The tackifier are by amino coupling agent, epoxy group coupling agent and polyisocyanate cyanogen
Ester compound is prepared.Compared with prior art, dealcoholized silicone rubber sealant provided by the invention uses specific thickening
Agent, coordinates other certain content components, realizes preferable interaction, and product is made to have preferable greenhouse curing performance and long-term
Storage stability, and it is excellent in adhesion, bonding persistence it is good.The experimental results showed that dealcoholized type silicon rubber provided by the invention
Glue sealant all has good caking property, can be used in photovoltaic module, build to metal, various plastics, ceramics, the materials such as glass
It builds and the sealings such as automobile and electronic apparatus.
In addition, preparation method provided by the invention is easy to operate, mild condition, it is suitable for large-scale production and application.
Specific implementation mode
Below in conjunction with the embodiment of the present invention, technical scheme of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Every other embodiment obtained by those of ordinary skill in the art without making creative efforts, belongs to this hair
The range of bright protection.
The present invention provides a kind of dealcoholized silicone rubber sealants, including following components：
100 parts by weight of dimethyl silicone polymer；
The parts by weight of 20 parts by weight of calcium carbonate~200；
The parts by weight of 2 parts by weight of organosilicon cross-linking agent~12；
The parts by weight of 0.05 parts by weight of catalyst~8；
The parts by weight of 0.05 parts by weight of tackifier~5；
The tackifier are prepared by amino coupling agent, epoxy group coupling agent and polyisocyanate compound.
In the present invention, the dimethyl silicone polymer preferably includes the compound of general formula and/or formula (II) shown in formula (I)
The compound of shown general formula；
HO(SiMe2O)nH formulas (I)；
(R2O)3-mR1 mSi-Z-(SiMe2O)nSiMe2-Z-SiR1 m(OR2)3-mFormula (II)；
Wherein, n be when the viscosity of dimethyl silicone polymer being made to be 200mPas~1000000mPas at 25 DEG C just
Number；R1And R2It is independent to be selected from monovalent hydrocarbon or alkoxyalkyl；M=0 or 1；Z is oxygen or bivalent hydrocarbon radical.
In the present invention, the dimethyl silicone polymer preferably includes the compound of general formula and/or formula (II) shown in formula (I)
The compound of general formula shown in the compound of shown general formula, more preferably formula (I).In the present invention, the dimethyl silicone polymer
The preferably compound of general formula shown in formula (I)；
HO(SiMe2O)nH formulas (I)；
Wherein, n is that the viscosity of dimethyl silicone polymer (compound of general formula shown in formula (I)) is made to be 200mPa at 25 DEG C
Positive number when s~1000000mPas.It follows that the dimethyl silicone polymer is preferably α, alpha, omega-dihydroxy polydimethyl
Siloxanes；The kinematic viscosity of the α, alpha, omega-dihydroxy polydimethyl siloxane are preferably 1500mm2/ s~80000mm2/ s, it is more excellent
It is selected as 2000mm2/ s~50000mm2/s.For the present invention to the α, the source of alpha, omega-dihydroxy polydimethyl siloxane is not special
Limitation, is prepared into using commercial goods well known to those skilled in the art or according to preparation method well known to those skilled in the art
The own product arrived.
In the present invention, the dimethyl silicone polymer is preferably the compound of general formula shown in formula (II)；
(R2O)3-mR1 mSi-Z-(SiMe2O)nSiMe2-Z-SiR1 m(OR2)3-mFormula (II)；
Wherein, n is to make the viscosity of dimethyl silicone polymer (compound of general formula shown in formula (II)) be at 25 DEG C
Positive number when 200mPas~1000000mPas；R1And R2It is independent to be selected from monovalent hydrocarbon or alkoxyalkyl；M=0 or 1；
Z is oxygen or bivalent hydrocarbon radical.
Preferably, R1And R2It is ethyl (Et), m=0；
When Z is-CH2CH2When, there is general formula shown in formula (II-1)；
(EtO)3SiCH2CH2-(SiMe2O)nSiMe2CH2CH2Si(OEt)3Formula (II-1).
It follows that the compound with general formula shown in formula (II) is preferably α, ω-triethoxy silicon substrate ethyl capping
Dimethyl silicone polymer；The kinematic viscosity of the dimethyl silicone polymer of the α, ω-triethoxy silicon substrate ethyl capping is preferably
1500mm2/ s~80000mm2/ s, more preferably 2000mm2/ s~50000mm2/s.The present invention is to the α, ω-triethoxy
The source of the dimethyl silicone polymer of silicon substrate ethyl capping is not particularly limited, using commercially available quotient well known to those skilled in the art
Product or the own product being prepared according to preparation method well known to those skilled in the art.
When Z is oxygen (- O-), there is general formula shown in formula (II-2)；
(EtO)3SiO(SiMe2O)nSiMe2OSi(OEt)3Formula (II-2).
Preferably, R1And R2It is methyl (Me), m=0；
When Z is-CH2CH2When, there is general formula shown in formula (II-3)；
(MeO)3SiCH2CH2-(SiMe2O)nSiMe2CH2CH2Si(OMe)3Formula (II-3)
Preferably, R1And R2It is methyl (Me), m=1；
When Z is-CH2CH2When, there is general formula shown in formula (II-4)；
(MeO)2MeSiCH2CH2-(SiMe2O)nSiMe2CH2CH2SiMe(OMe)2Formula (II-4).
When Z is oxygen (- O-), there is general formula shown in formula (II-5)；
(MeO)2MeSiO(SiMe2O)nSiMe2OSiMe(OMe)2Formula (II-5).
The present invention uses above-mentioned dimethyl silicone polymer for basic sizing material.In the present invention, the dimethyl silicone polymer
Kinematic viscosity be preferably 1500mm2/ s~80000mm2/ s, more preferably 2000mm2/ s~50000mm2/s。
In the present invention, the dimethyl silicone polymer preferably further includes poly- the two of Alpha-hydroxy-ω-trimethyl silicon substrate sealing end
The dimethyl silicone polymer of methylsiloxane and/or α-triethoxy silicon substrate ethyl-ω-trimethyl silicon substrate sealing end.In the present invention
In, the kinematic viscosity of the dimethyl silicone polymer of the Alpha-hydroxy-ω-trimethyl silicon substrate sealing end is preferably 1500mm2/ s~
80000mm2/ s, more preferably 2000mm2/ s~50000mm2/s；The α-triethoxy silicon substrate ethyl-ω-trimethyl silicon substrate
The kinematic viscosity of the dimethyl silicone polymer of sealing end is preferably 1500mm2/ s~80000mm2/ s, more preferably 2000mm2/ s~
50000mm2/s.Dimethyl silicone polymer and α-triethoxysilicane of the present invention to the Alpha-hydroxy-ω-trimethyl silicon substrate sealing end
The source of the dimethyl silicone polymer of base ethyl-ω-trimethyl silicon substrate sealing end is not particularly limited, using those skilled in the art
Well known commercial goods or the own product being prepared according to preparation method well known to those skilled in the art.
In the present invention, the dimethyl silicone polymer is including the compound of general formula shown in formula (I) and/or formula (II) institute
Further include the dimethyl silicone polymer and/or α-three of Alpha-hydroxy-ω-trimethyl silicon substrate sealing end on the basis of showing the compound of general formula
The dimethyl silicone polymer of ethyl-silicone ethyl-ω-trimethyl silicon substrate sealing end；The present invention is with the chemical combination of general formula shown in formula (I)
The compound of general formula shown in object and/or formula (II) is base rubber, the poly dimethyl silicon of addition Alpha-hydroxy-ω-trimethyl silicon substrate sealing end
The dimethyl silicone polymer of oxygen alkane and/or α-triethoxy silicon substrate ethyl-ω-trimethyl silicon substrate sealing end, is used in mixed way, Neng Gouda
To the low modulus of glue, soft, high elongation rate and the purpose for reducing free silicone oil.
In the preferred embodiment of the invention, the dimethyl silicone polymer is the compound and α-of general formula shown in formula (I)
The dimethyl silicone polymer of hydroxyl-ω-trimethyl silicon substrate sealing end；The compound and Alpha-hydroxy-ω-of general formula shown in the formula (I)
The mass ratio of the dimethyl silicone polymer of trimethyl silicon substrate sealing end is preferably 40：(50~70), more preferably 40：60.
In presently preferred embodiment, the dimethyl silicone polymer is the chemical combination of general formula shown in formula (II)
The dimethyl silicone polymer of object and α-triethoxy silicon substrate ethyl-ω-trimethyl silicon substrate sealing end；General formula shown in the formula (II)
The mass ratio of the dimethyl silicone polymer of compound and α-triethoxy silicon substrate ethyl-ω-trimethyl silicon substrate sealing end is preferably 40：
(50~70), more preferably 40：60.
In the present invention, the dealcoholized silicone rubber sealant includes the dimethyl silicone polymer of 100 parts by weight.
In the present invention, the calcium carbonate is preferably selected from one in nano-calcium carbonate, precipitated calcium carbonate and powdered whiting
Kind is a variety of, more preferably nano-calcium carbonate.In the preferred embodiment of the invention, the calcium carbonate is nano-calcium carbonate, institute
The particle size range for stating nano-calcium carbonate is 50nm~100nm；The present invention use above-mentioned nano-calcium carbonate, be conducive to its be distributed to it is close
It seals in the rubber of agent, to provide strengthening action.In the preferred embodiment of the invention, the calcium carbonate be precipitated calcium carbonate and
Powdered whiting；The present invention preferably carries out fatty acid surface processing to above-mentioned calcium carbonate, can equally improve it in rubber
Dispersibility.The present invention is not particularly limited the source of the calcium carbonate, using commercial goods well known to those skilled in the art
Or own product.
The present invention uses above-mentioned calcium carbonate for solid packing.In the present invention, the dealcoholized silicone rubber sealant includes
The calcium carbonate of the parts by weight of 20 parts by weight~200, the parts by weight of preferably 100 parts by weight~125, more preferably 120 parts by weight.
In addition, the present invention under the premise of not influencing properties of product, can also add widely applied additive in silicon rubber；
Inorganic additive, mould inhibitor, fire retardant, heat-resistant agent, mill base, thickener such as in addition to the calcium carbonate.
In the present invention, it is last, hollow to be preferably selected from white carbon, quartz micropowder for the inorganic additive in addition to the calcium carbonate
In glass microsphere, diatomite, titanium dioxide, aluminium hydroxide, aluminium oxide, zinc oxide, magnesia, the sub- zinc of oxidation and carbonic acid Asia zinc
It is one or more, more preferably white carbon；Above-mentioned inorganic additive preferably uses organosilicon alkanes, silazane class, siloxane oligomer
Object etc. is surface-treated, to improving its dispersibility in rubber.
In the present invention, the mill base primarily serve toning effect, those skilled in the art can according to border use demand,
Select the color of mill base, such as black slurry, stock white, silver color slurry.
The present invention is not particularly limited the source of above-mentioned additive, using commercial goods well known to those skilled in the art
Or own product.In the present invention, additive amount of the additive in the dealcoholized silicone rubber sealant is no more than 10
Parts by weight.
In the present invention, the organosilicon cross-linking agent is preferably selected from methyltrimethoxysilane, vinyl trimethoxy silicon
Alkane, methyltriethoxysilane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, trimethoxysilane,
It is one or more in isobutyl triethoxy silane, methyl orthosilicate and ethyl orthosilicate, more preferably methyl trimethoxy oxygroup
Silane and/or trimethoxysilane.The present invention is not particularly limited the source of the organosilicon cross-linking agent, using this
Commercial goods known to field technology personnel.
The present invention makes sealant become elasticity after being reacted with sizing dimethyl silicone polymer using organosilicon cross-linking agent
Body, to realize that crosslinking curing acts on.In the present invention, the dealcoholized silicone rubber sealant includes the weight of 2 parts by weight~12
Part organosilicon cross-linking agent, the parts by weight of preferably 5 parts by weight~8.
In the present invention, the catalyst is preferably selected from one in titanium-containing catalyst, zirconium-containing catalyst and tin-containing catalyst
Kind is a variety of, more preferably titanium-containing catalyst.In the present invention, the titanium-containing catalyst is preferably selected from tetrabutyl titanate, metatitanic acid
It is one or more in isopropyl ester, the metatitanic acid tert-butyl ester and ethylacetoacetate titanium compound, more preferably ethylacetoacetate titanium
Compound.In the present invention, the zirconium-containing catalyst is preferably selected from zirconium-n-butylate, zirconic acid isopropyl ester, the zirconic acid tert-butyl ester, acetyl
One or more of acetone zirconium composite and ethyl acetoacetate zirconium compound.In the present invention, the tin-containing catalyst is excellent
Choosing is in dibutyl tin laurate, tin dilaurate dioctyl tin, two pungent capric acid stannous methides and dibutyltin diacetate
It is one or more.The present invention is not particularly limited the source of the catalyst, using well known to those skilled in the art commercially available
Commodity or own product.
In the present invention, the catalyst, which primarily serves, accelerates cured effect.In the present invention, the dealcoholized type silicon rubber
Glue sealant includes the catalyst of the parts by weight of 0.05 parts by weight~8, the parts by weight of preferably 3 parts by weight~6.
In the present invention, the tackifier are prepared by amino coupling agent, epoxy group coupling agent and polyisocyanate compound
It forms.In the present invention, the amino coupling agent be preferably selected from aminopropyl trimethoxysilane, aminopropyl triethoxysilane,
γ-aminoethyl amino propyl trimethoxy silane, γ-aminoethylaminopropyl triethoxysilane, bis- [3- (triethoxysilicane) third
Base] amine, bis- (3- trimethoxy-silylpropyls) amine, bis- [3- (trimethoxy silicon substrate) propyl] ethylenediamines and bis- [3- (three second
Oxygroup silicon substrate) propyl] ethylenediamine one or more, more preferably aminopropyl trimethoxysilane.The present invention is to the amino
The source of coupling agent is not particularly limited, using commercial goods well known to those skilled in the art.
In the present invention, the epoxy group coupling agent be preferably selected from γ-glycidyl ether oxygen propyl trimethoxy silicane,
γ-glycidoxypropyltrietandysilane andysilane, γ-glycidyl ether oxygen propyl methyldiethoxysilane, γ-shrink are sweet
Oily ether oxygen propyl methyl dimethoxysilane, β-(3,4- 7-oxa-bicyclo[4.1.0) ethyl trimethoxy silane it is one or more, more
Preferably γ-glycidyl ether oxygen propyl trimethoxy silicane.The present invention is not special to the source of the epoxy group coupling agent
Limitation, using commercial goods well known to those skilled in the art.
In the present invention, it is different to be preferably selected from toluene di-isocyanate(TDI), diphenyl methane two for the polyisocyanate compound
Cyanate, hexamethylene diisocyanate, hexamethylene diisocyanate tripolymer and one kind in isoflurane chalcone diisocyanate or
It is a variety of, more preferably 1, hexamethylene-diisocyanate.The present invention is not particularly limited the source of the polyisocyanate compound,
Using commercial goods well known to those skilled in the art.
In the present invention, the tackifier are preferably 1 by molar ratio：2：Amino coupling agent, the epoxy group of (0.2~3) are even
Connection agent and polyisocyanate compound are prepared, and are more preferably 1 by molar ratio：2：Amino coupling agent, the epoxy group of (1~2)
Coupling agent and polyisocyanate compound are prepared.
In the present invention, the preparation method of the tackifier is preferably specially：
Amino coupling agent, epoxy group coupling agent and polyisocyanate compound are mixed, is reacted, obtains tackifier.
In the present invention, the temperature of the reaction is preferably 20 DEG C~60 DEG C, more preferably 25 DEG C~50 DEG C；The time of the reaction is excellent
It is selected as 48h~680h, more preferably 110h~672h.In the preferred embodiment of the invention, the condition of the reaction is specially：
Temperature is 25 DEG C, time 672h；In presently preferred embodiment, the condition of the reaction is specially：Temperature
It is 50 DEG C, time 110h.
The present invention uses specific tackifier, coordinates other certain content components, realizes preferable interaction, product is made to have
Have preferable greenhouse curing performance and a long-term storage stability, and it is excellent in adhesion, bonding persistence is good.In the present invention
In, the dealcoholized silicone rubber sealant includes the tackifier of the parts by weight of 0.05 parts by weight~5, preferably 0.5 parts by weight.
In the present invention, the dealcoholized silicone rubber sealant preferably further includes：
The parts by weight of 1 parts by weight of plasticizer~20, more preferably 10 parts by weight.In the present invention, the plasticizer is preferably
Dimethicone；The viscosity of the dimethicone is preferably 50mm2/ s~12000mm2/ s, more preferably 100mm2/ s~
5000mm2/s。
The present invention also provides a kind of preparation methods of the dealcoholized silicone rubber sealant described in above-mentioned technical proposal, including
Following steps：
A) amino coupling agent, epoxy group coupling agent and polyisocyanate compound are mixed, is reacted, is viscosified
Agent；
B) tackifier for obtaining dimethyl silicone polymer, calcium carbonate, organosilicon cross-linking agent, catalyst and step a) are mixed
It closes, dealcoholized silicone rubber sealant is obtained after discharging.
The present invention first mixes amino coupling agent, epoxy group coupling agent and polyisocyanate compound, is reacted, is obtained
To tackifier.In the present invention, the amino coupling agent is preferably selected from aminopropyl trimethoxysilane, aminopropyl-triethoxy silicon
Alkane, γ-aminoethyl amino propyl trimethoxy silane, γ-aminoethylaminopropyl triethoxysilane, bis- [3- (triethoxysilicane)
Propyl] amine, bis- (3- trimethoxy-silylpropyls) amine, bis- [3- (trimethoxy silicon substrate) propyl] ethylenediamines and bis- [3- (three
Ethyl-silicone) propyl] ethylenediamine one or more, more preferably aminopropyl trimethoxysilane.The present invention is to the ammonia
The source of base coupling agent is not particularly limited, using commercial goods well known to those skilled in the art.
In the present invention, the epoxy group coupling agent be preferably selected from γ-glycidyl ether oxygen propyl trimethoxy silicane,
γ-glycidoxypropyltrietandysilane andysilane, γ-glycidyl ether oxygen propyl methyldiethoxysilane, γ-shrink are sweet
Oily ether oxygen propyl methyl dimethoxysilane, β-(3,4- 7-oxa-bicyclo[4.1.0) ethyl trimethoxy silane it is one or more, more
Preferably γ-glycidyl ether oxygen propyl trimethoxy silicane.The present invention is not special to the source of the epoxy group coupling agent
Limitation, using commercial goods well known to those skilled in the art.
In the present invention, it is different to be preferably selected from toluene di-isocyanate(TDI), diphenyl methane two for the polyisocyanate compound
Cyanate, hexamethylene diisocyanate, hexamethylene diisocyanate tripolymer and one kind in isoflurane chalcone diisocyanate or
It is a variety of, more preferably 1, hexamethylene-diisocyanate.The present invention is not particularly limited the source of the polyisocyanate compound,
Using commercial goods well known to those skilled in the art.
In the present invention, the molar ratio of the amino coupling agent, epoxy group coupling agent and polyisocyanate compound is preferred
It is 1：2：(0.2~3), more preferably 1：2：(1~2).
In the present invention, the temperature of the reaction is preferably 20 DEG C~60 DEG C, more preferably 25 DEG C~50 DEG C；The reaction
Time be preferably 48h~680h, more preferably 110h~672h.In the preferred embodiment of the invention, the item of the reaction
Part is specially：Temperature is 25 DEG C, time 672h；In presently preferred embodiment, the condition of the reaction has
Body is：Temperature is 50 DEG C, time 110h.
After obtaining the tackifier, the present invention by dimethyl silicone polymer, calcium carbonate, organosilicon cross-linking agent, catalyst and
The tackifier mixing that step a) is obtained, obtains dealcoholized silicone rubber sealant after discharging.The present invention does not have the equipment of the mixing
Have it is specifically limited, using high speed dispersion planet machine well known to those skilled in the art.
In the present invention, the process of the mixing is preferably specially：
Dimethyl silicone polymer and calcium carbonate are mixed, mixed material is obtained；It adds organosilicon cross-linking agent and urges
Agent stirs evenly under vacuum, is eventually adding tackifier and is stirred evenly under vacuum or disconnected moist conditions, after discharging
To dealcoholized silicone rubber sealant.
In the preferred embodiment of the invention, the dimethyl silicone polymer includes the chemical combination with general formula shown in formula (I)
Object；In the case, while it mixing with calcium carbonate, 100 DEG C~150 DEG C are preferably heated to, -0.09MPa~-
Vacuum dehydration 2h~4h under 0.1MPa, obtains mixed material；Be more preferably heated to 120 DEG C~130 DEG C, -0.09MPa~-
Vacuum dehydration 3h under 0.1MPa, obtains mixed material.Also, said mixture material adds organosilicon when being cooled to 50 DEG C or less
Crosslinking agent and catalyst carry out subsequent process.
In addition, the present invention under the premise of not influencing properties of product, can also add widely applied additive in silicon rubber；
Inorganic additive, mould inhibitor, fire retardant, heat-resistant agent, mill base, thickener such as in addition to the calcium carbonate.In the present invention, above-mentioned
The adition process of additive preferably it is described dimethyl silicone polymer and calcium carbonate are mixed during carry out.
The present invention provides a kind of dealcoholized silicone rubber sealants, including following components：100 weight of dimethyl silicone polymer
Part；The parts by weight of 20 parts by weight of calcium carbonate~200；The parts by weight of 2 parts by weight of organosilicon cross-linking agent~12；0.05 parts by weight of catalyst~
8 parts by weight；The parts by weight of 0.05 parts by weight of tackifier~5；The tackifier are by amino coupling agent, epoxy group coupling agent and polyisocyanate cyanogen
Ester compound is prepared.Compared with prior art, dealcoholized silicone rubber sealant provided by the invention uses specific thickening
Agent, coordinates other certain content components, realizes preferable interaction, and product is made to have preferable greenhouse curing performance and long-term
Storage stability, and it is excellent in adhesion, bonding persistence it is good.The experimental results showed that dealcoholized type silicon rubber provided by the invention
Glue sealant all has good caking property, can be used in photovoltaic module, build to metal, various plastics, ceramics, the materials such as glass
It builds and the sealings such as automobile and electronic apparatus.
In addition, preparation method provided by the invention is easy to operate, mild condition, it is suitable for large-scale production and application.
In order to further illustrate the present invention, it is described in detail below by following embodiment.Following embodiment of the present invention
The kinematic viscosity of α used, alpha, omega-dihydroxy polydimethyl siloxane are 20000mm2/s；Nano-calcium carbonate used is by Zhejiang
Tian Shi nanosecond science and technology limited liability company provides, and particle size range is 50nm~100nm；Alpha-hydroxy-ω used-trimethyl silicon substrate
The kinematic viscosity of the dimethyl silicone polymer of sealing end is 20000mm2/ s is indicated with formula (III-1)：
Me-(SiMe2O)n+2H formulas (III-1)；
The kinematic viscosity of the dimethyl silicone polymer of α used, ω-triethoxy silicon substrate ethyl capping is 10000mm2/
S is indicated with formula (II-1)：
(EtO)3SiCH2CH2-(SiMe2O)nSiMe2CH2CH2Si(OEt)3Formula (II-1)；
The kinematic viscosity of the dimethyl silicone polymer of α used-triethoxy silicon substrate ethyl-ω-trimethyl silicon substrate sealing end
For 10000mm2/ s is indicated with formula (III-2)：
Me-(SiMe2O)nSiMe2CH2CH2Si(OMe)3Formula (III-2)；
Precipitated calcium carbonate used is the precipitated calcium carbonate of fatty acid surface processing；Powdered whiting used is to grind carbon
Sour calcium.
Embodiment 1
(1) by oneself two isocyanides of aminopropyl trimethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane and 1,6-
Acid esters is according to molar ratio 1：2：2 mixing, react 110h at 50 DEG C, obtain tackifier.
(2) by the α of 100 parts by weight, alpha, omega-dihydroxy polydimethyl siloxane, the dimethicone of 10 parts by weight, 120 weights
The stock white of the nano-calcium carbonate and 8 parts by weight of measuring part, which is put into high speed dispersion planet machine, to be stirred, while heated to 120
DEG C, the vacuum dehydration 3h at -0.09MPa~-0.1MPa obtains dewatered mixed material；Then said mixture material is dropped
Temperature to 50 DEG C hereinafter, be added 8 parts by weight methyltrimethoxysilane and 6 parts by weight ethylacetoacetate titanium compound,
It being stirred evenly under vacuum condition, adds the tackifier of 0.5 parts by weight, continuation stirs evenly under vacuum, after discharging
To dealcoholized silicone rubber sealant.
Embodiment 2
(1) by oneself two isocyanides of aminopropyl trimethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane and 1,6-
Acid esters is according to molar ratio 1：2：1.5 mixing, react 110h at 50 DEG C, obtain tackifier.
(2) by the α of 40 parts by weight, alpha, omega-dihydroxy polydimethyl siloxane, 60 parts by weight Alpha-hydroxy-ω-trimethyl silicane
Dimethyl silicone polymer, the nano-calcium carbonate of 120 parts by weight and the stock white of 8 parts by weight of base sealing end put into high speed dispersion row
It is stirred in star machine, while heated to 120 DEG C, the vacuum dehydration 3h at -0.09MPa~-0.1MPa, it obtains dewatered mixed
Close material；Then said mixture material is cooled to 50 DEG C hereinafter, the methyltrimethoxysilane and 6 weight of 8 parts by weight is added
The ethylacetoacetate titanium compound of part, stirs evenly, adds the tackifier of 0.5 parts by weight under vacuum, disconnected wet
It is stirred evenly under the conditions of gas, dealcoholized silicone rubber sealant is obtained after discharging.
Embodiment 3
(1) by oneself two isocyanides of aminopropyl trimethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane and 1,6-
Acid esters is according to molar ratio 1：2：1 mixing, reacts 110h at 50 DEG C, obtains tackifier.
(2) by the α of 40 parts by weight, the dimethyl silicone polymer of ω-triethoxy silicon substrate ethyl capping, the α-of 60 parts by weight
The dimethyl silicone polymer of triethoxy silicon substrate ethyl-ω-trimethyl silicon substrate sealing end, the precipitated calcium carbonate and 25 of 100 parts by weight
The powdered whiting of parts by weight, which is put into high speed dispersion planet machine, to be stirred uniformly, and mixed material is obtained；Then above-mentioned
The methyltrimethoxysilane of 2.5 parts by weight, the trimethoxysilane of 2.5 parts by weight and 3 weights are added in mixed material
The ethylacetoacetate titanium compound for measuring part, stirs evenly, adds the tackifier of 0.5 parts by weight under vacuum, disconnected
It is stirred evenly under moist conditions, dealcoholized silicone rubber sealant is obtained after discharging.
Comparative example 1
By the α of 100 parts by weight, alpha, omega-dihydroxy polydimethyl siloxane, the dimethicone of 10 parts by weight, 120 parts by weight
Nano-calcium carbonate and the stock whites of 8 parts by weight put into high speed dispersion planet machine and be stirred, while heated to 120 DEG C,
The vacuum dehydration 3h at -0.09MPa~-0.1MPa obtains dewatered mixed material；Then said mixture material is cooled to
50 DEG C hereinafter, be added the ethylacetoacetate titanium compound of the methyltrimethoxysilane and 6 parts by weight of 8 parts by weight, in vacuum
Under the conditions of stir evenly, dealcoholized silicone rubber sealant is obtained after discharging.
Comparative example 2
By the α of 100 parts by weight, alpha, omega-dihydroxy polydimethyl siloxane, the dimethicone of 10 parts by weight, 120 parts by weight
Nano-calcium carbonate and the stock whites of 8 parts by weight put into high speed dispersion planet machine and be stirred, while heated to 120 DEG C,
The vacuum dehydration 3h at -0.09MPa~-0.1MPa obtains dewatered mixed material；Then said mixture material is cooled to
50 DEG C hereinafter, be added the ethylacetoacetate titanium compound of the methyltrimethoxysilane and 6 parts by weight of 8 parts by weight, in vacuum
Under the conditions of stir evenly, add the hexamethyldisilazane of 0.5 parts by weight, continuation stirs evenly under vacuum, discharges
After obtain dealcoholized silicone rubber sealant.
Comparative example 3
By the α of 100 parts by weight, alpha, omega-dihydroxy polydimethyl siloxane, the dimethicone of 10 parts by weight, 120 parts by weight
Nano-calcium carbonate and the stock whites of 8 parts by weight put into high speed dispersion planet machine and be stirred, while heated to 120 DEG C,
The vacuum dehydration 3h at -0.09MPa~-0.1MPa obtains dewatered mixed material；Then said mixture material is cooled to
50 DEG C hereinafter, be added the ethylacetoacetate titanium compound of the methyltrimethoxysilane and 6 parts by weight of 8 parts by weight, in vacuum
Under the conditions of stir evenly, add the aminopropyl trimethoxysilane of 0.5 parts by weight, continuation stirs evenly under vacuum,
Dealcoholized silicone rubber sealant is obtained after discharging.
Comparative example 4
By the α of 100 parts by weight, alpha, omega-dihydroxy polydimethyl siloxane, the dimethicone of 10 parts by weight, 120 parts by weight
Nano-calcium carbonate and the stock whites of 8 parts by weight put into high speed dispersion planet machine and be stirred, while heated to 120 DEG C,
The vacuum dehydration 3h at -0.09MPa~-0.1MPa obtains dewatered mixed material；Then said mixture material is cooled to
50 DEG C hereinafter, be added the ethylacetoacetate titanium compound of the methyltrimethoxysilane and 6 parts by weight of 8 parts by weight, in vacuum
Under the conditions of stir evenly, add γ-glycidyl ether oxygen propyl trimethoxy silicane of 0.5 parts by weight, continue in vacuum item
It is stirred evenly under part, dealcoholized silicone rubber sealant is obtained after discharging.
To curing performance, the initial bond of the dealcoholized silicone rubber sealant that Examples 1 to 3 and comparative example 1~4 provide
And bonding persistence is tested, the specific method is as follows：
Viscosity is measured at 25 degree.
Initial bond：Glass plate, metallic plate (aluminium, stainless steel, copper coin) and plastic plate (ethylene chloride resin, PC,
PMC etc.) surface on dealcoholized silicone rubber sealant is squeezed out linear, cured under conditions of 25 DEG C, humidity 50%, put
It sets 3 days；Then from cured colloid one end with pull make colloid remove substrate, measure cementability；Measurement result is with side below
Method indicates：
Zero print：Organosilicon colloid fracture (agglutination destructive rate 100%)；
△ prints：The interface peel (agglutination destructive rate 50~99%) of some organosilicon colloid layer and substrate；
× print：The interface peel (agglutination destructive rate 0~49%) of big a part of organosilicon colloid layer and substrate.
It is bonded persistence：Glass plate, metallic plate (aluminium, stainless steel, copper coin) and plastic plate (ethylene chloride resin, PC,
PMC etc.) surface on dealcoholized silicone rubber sealant is squeezed out linear, cured under conditions of 25 DEG C, humidity 50%, put
It sets 3 days；Then test body is put into 25 DEG C of water and is placed 3 days；Then test body is taken out from water, then from cured colloid
One end makes colloid and strippable substrate with pulling, and measures cementability；Measurement result is indicated with the following method：
Zero print：Organosilicon colloid fracture (agglutination destructive rate 100%)；
△ prints：The interface peel (agglutination destructive rate 50~99%) of some organosilicon colloid layer and substrate；
× print：The interface peel (agglutination destructive rate 0~49%) of big a part of organosilicon colloid layer and substrate.
After tested, the curing performance for the dealcoholized silicone rubber sealant that Examples 1 to 3 and comparative example 1~4 provide, initial stage
Cementability and the persistent data of bonding are referring to shown in table 1~2.
The curing performance and initial bond for the dealcoholized silicone rubber sealant that 1 Examples 1 to 3 of table and comparative example 1~4 provide
Property data
The bonding persistent data for the dealcoholized silicone rubber sealant that 2 Examples 1 to 3 of table and comparative example 1~4 provide
By table 1~2 it is found that there is the dealcoholized silicone rubber sealant that the embodiment of the present invention 1~3 provides preferable greenhouse to consolidate
Change performance and long-term storage stability, and it is excellent in adhesion, bonding persistence is good；To metal (such as stainless steel, cold after solidification
Steel rolling, aluminium, copper, anodised aluminium etc.), various plastics (such as PC, PMMA, ABS, PET), ceramics, the materials such as glass all have
Good caking property can be used in photovoltaic module, building and the sealings such as automobile and electronic apparatus.
The above description of the disclosed embodiments, enables those skilled in the art to implement or use the present invention.It is right
A variety of modifications of these embodiments will be apparent to those skilled in the art, and as defined herein one
As principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will
It will not be intended to be limited to the embodiments shown herein, and be to fit to consistent with the principles and novel features disclosed herein
Widest range.
Claims (10)
1. a kind of dealcoholized silicone rubber sealant, including following components：
100 parts by weight of dimethyl silicone polymer；
The parts by weight of 20 parts by weight of calcium carbonate~200；
The parts by weight of 2 parts by weight of organosilicon cross-linking agent~12；
The parts by weight of 0.05 parts by weight of catalyst~8；
The parts by weight of 0.05 parts by weight of tackifier~5；
The tackifier are prepared by amino coupling agent, epoxy group coupling agent and polyisocyanate compound.
2. dealcoholized silicone rubber sealant according to claim 1, which is characterized in that the dimethyl silicone polymer includes
The compound of general formula shown in the compound of general formula and/or formula (II) shown in formula (I)；
HO(SiMe2O)nH formulas (I)；
(R2O)3-mR1 mSi-Z-(SiMe2O)nSiMe2-Z-SiR1 m(OR2)3-mFormula (II)；
Wherein, n is the positive number when viscosity of dimethyl silicone polymer being made to be 200mPas~1000000mPas at 25 DEG C；R1
And R2It is independent to be selected from monovalent hydrocarbon or alkoxyalkyl；M=0 or 1；Z is oxygen or bivalent hydrocarbon radical.
3. dealcoholized silicone rubber sealant according to claim 2, which is characterized in that the dimethyl silicone polymer also wraps
Include the dimethyl silicone polymer and/or α-triethoxy silicon substrate ethyl-ω-trimethyl silicane of Alpha-hydroxy-ω-trimethyl silicon substrate sealing end
The dimethyl silicone polymer of base sealing end.
4. dealcoholized silicone rubber sealant according to claim 1, which is characterized in that the organosilicon cross-linking agent is selected from first
Base trimethoxy silane, vinyltrimethoxysilane, methyltriethoxysilane, isopropyltri-methoxysilane, isopropyl
In triethoxysilane, trimethoxysilane, isobutyl triethoxy silane, methyl orthosilicate and ethyl orthosilicate
It is one or more.
5. dealcoholized silicone rubber sealant according to claim 1, which is characterized in that the amino coupling agent is selected from ammonia third
Base trimethoxy silane, aminopropyl triethoxysilane, γ-aminoethyl amino propyl trimethoxy silane, γ-aminoethylaminopropyl
Triethoxysilane, bis- [3- (triethoxysilicane) propyl] amine, bis- (3- trimethoxy-silylpropyls) amine, bis- [3- (front threes
Oxygroup silicon substrate) propyl] ethylenediamine and bis- [3- (triethoxy silicon substrate) propyl] ethylenediamines it is one or more.
6. dealcoholized silicone rubber sealant according to claim 1, which is characterized in that the epoxy group coupling agent is selected from
γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-glycidoxypropyltrietandysilane andysilane, γ-glycidol ether
Oxygen propyl group methyldiethoxysilane, γ-glycidyl ether oxygen propyl methyl dimethoxysilane, β-(3,4- 7-oxa-bicyclo[4.1.0s)
Ethyl trimethoxy silane it is one or more.
7. dealcoholized silicone rubber sealant according to claim 1, which is characterized in that the polyisocyanate compound choosing
From toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate tripolymer
With it is one or more in isoflurane chalcone diisocyanate.
8. dealcoholized silicone rubber sealant according to claim 1, which is characterized in that the tackifier are 1 by molar ratio：
2：Amino coupling agent, epoxy group coupling agent and the polyisocyanate compound of (0.2~3) are prepared.
9. a kind of preparation method of claim 1~8 any one of them dealcoholized silicone rubber sealant, includes the following steps：
A) amino coupling agent, epoxy group coupling agent and polyisocyanate compound are mixed, is reacted, obtains tackifier；
B) tackifier for obtaining dimethyl silicone polymer, calcium carbonate, organosilicon cross-linking agent, catalyst and step a) mix, and go out
Dealcoholized silicone rubber sealant is obtained after material.
10. preparation method according to claim 9, which is characterized in that the temperature reacted described in step a) be 20 DEG C~
60 DEG C, the time is 48h~680h.
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| CN110982480A (en) * | 2019-12-10 | 2020-04-10 | 广州市白云化工实业有限公司 | Single-component flame-retardant high-temperature-resistant silicone sealant and preparation method thereof |
| CN112724922A (en) * | 2020-12-28 | 2021-04-30 | 广州市白云化工实业有限公司 | High-temperature anti-yellowing organic silicon bonding sealant and preparation method thereof |
| CN112961645A (en) * | 2021-02-09 | 2021-06-15 | 佛山东麓科技有限公司 | Self-curing insulating silicone rubber and preparation method and application thereof |
| CN114507504A (en) * | 2022-01-14 | 2022-05-17 | 杭州之江有机硅化工有限公司 | Low-modulus high-elongation single-component organosilicon sealant and application thereof |
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| CN110982480A (en) * | 2019-12-10 | 2020-04-10 | 广州市白云化工实业有限公司 | Single-component flame-retardant high-temperature-resistant silicone sealant and preparation method thereof |
| CN112724922A (en) * | 2020-12-28 | 2021-04-30 | 广州市白云化工实业有限公司 | High-temperature anti-yellowing organic silicon bonding sealant and preparation method thereof |
| CN112724922B (en) * | 2020-12-28 | 2022-04-26 | 广州市白云化工实业有限公司 | High-temperature anti-yellowing organic silicon bonding sealant and preparation method thereof |
| CN112961645A (en) * | 2021-02-09 | 2021-06-15 | 佛山东麓科技有限公司 | Self-curing insulating silicone rubber and preparation method and application thereof |
| CN114507504A (en) * | 2022-01-14 | 2022-05-17 | 杭州之江有机硅化工有限公司 | Low-modulus high-elongation single-component organosilicon sealant and application thereof |
| CN114507504B (en) * | 2022-01-14 | 2023-12-29 | 杭州之江有机硅化工有限公司 | Low-modulus high-elongation single-component organic silicon sealant and application thereof |
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